CN105601766A - Method for preparing full-acylation hemicellulose at room temperature and homogeneous phase - Google Patents
Method for preparing full-acylation hemicellulose at room temperature and homogeneous phase Download PDFInfo
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- CN105601766A CN105601766A CN201610010297.9A CN201610010297A CN105601766A CN 105601766 A CN105601766 A CN 105601766A CN 201610010297 A CN201610010297 A CN 201610010297A CN 105601766 A CN105601766 A CN 105601766A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
- C08B37/14—Hemicellulose; Derivatives thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
- C08B37/0003—General processes for their isolation or fractionation, e.g. purification or extraction from biomass
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Abstract
The invention belongs to the technical field of biomass material modification and discloses a method for preparing full-acylation hemicellulose at room temperature and a homogeneous phase. The preparation method comprises the steps that hemicellulose is dissolved in a mixed solvent of dimethyl sulfoxide and N-methylimidazole to obtain a hemicellulose solution, and then an acylation reagent is added for an esterification reaction at the room temperature; after the esterification reaction is over, the obtained solution is poured in a precipitator for precipitation, and the full-acylation hemicellulose is obtained after filtering, washing and freeze drying. The preparation method is implemented at the room temperature and the homogeneous phase, there is no need to add any catalyst in the reaction process, reaction conditions are simple, economical and environmentally friendly, reaction efficiency is high, and technical support is provided for development and utilization of the hemicellulose.
Description
Technical field
The invention belongs to modified by biomass materials technical field, be specifically related to a kind of room temperature homogeneous phase and prepare full acidylateThe method of hemicellulose.
Background technology
Hemicellulose is one of three large components of agricultural-forestry biomass resource, is only second to fibre at the content of occurring in natureDimension element, accounts for the 20-40% of plant resources total amount, has cheap and easy to get, renewable, biodegradable etc. excellentPoint. Along with the attention of people to environmental problem and the fast development of Green Chemistry, adopt renewable resource systemThe material of standby function admirable has inevitably become development trend from now on. But due to structure heterogeneity,The shortcomings such as low polymerization degree, low-molecular-weight, strongly hydrophilic, the development and utilization of double cellulose resource still has very muchLimit. Chemical modification is a kind of effective method, can make up the intrinsic defect of hemicellulose, for to greatest extentUtilize hemicellulose that chance is provided.
Homogeneous phase esterification modification is simply a kind of and effectively prepares the method for hemicellulose derivative, can be obviousImprove hemicellulose performance, such as heat endurance, homogeneity, dissolubility and hydrophily etc. By derivativeChange reaction, can produce the hemicellulose derivative of multiple function admirable, in agricultural, biological and chemistryizationThe fields such as work have broad application prospects. Half-and-half cellulosic esterification modification was mainly at high temperature and needed in the pastAdd and carry out under the condition of catalyst, reaction condition is complicated and higher to energy demand, and reaction obtainsHemicellulose derivatization degree is not high, does not meet the general orientation of modern sustainable economic development.
Summary of the invention
In order to solve the shortcoming and defect part of above prior art, the object of the present invention is to provide a kind of chamberTemperature homogeneous phase is prepared the method for full acidylate hemicellulose.
The object of the invention is achieved through the following technical solutions:
Room temperature homogeneous phase is prepared a method for full acidylate hemicellulose, comprises following preparation process:
Hemicellulose is dissolved in the mixed solvent of dimethyl sulfoxide (DMSO) and N-methylimidazole, obtains hemicelluloseSolution, then adds acylating reagent, carries out esterification under room temperature; After esterification finishes, by what obtainSolution is poured in precipitating reagent and is precipitated, and filters, and washing, obtains full acidylate hemicellulose after freeze drying.
Preferably, xylan quality percentage composition >=55% in described hemicellulose.
Preferably, the solution temperature that described hemicellulose is dissolved in mixed solvent is 60～120 DEG C, when dissolvingBetween be 0.5～6h.
Preferably, the mass volume ratio of described hemicellulose and mixed solvent is 1:(5～30) g/mL.
Preferably, dimethyl sulfoxide (DMSO) in the mixed solvent of described dimethyl sulfoxide (DMSO) and N-methylimidazole: N-methyl miaowThe volume ratio of azoles is (0.5～10): 1.
Preferably, described acylating reagent be acetic anhydride, propionic andydride, butyric anhydride, chloroacetic chloride, propionyl chloride andAny one in butyl chloride.
Preferably, in described acylating reagent and hemicellulose, the mol ratio of contained wood sugar unit is (0.5～20): 1.
Preferably, the time of described esterification is 0.5～48h, and course of reaction keeps uniform stirring.
Preferably, described precipitating reagent refers to water; The addition of described precipitating reagent is reaction gained liquor capacity5～10 times.
Preferably, described washing refers to the washing of dialysing in water.
Preparation method's tool of the present invention has the following advantages and beneficial effect:
(1) preparation method of the present invention at room temperature carries out, and without heating, requires low to equipment and the energy;
(2) preparation method of the present invention implements under homogeneous phase condition, and reaction is easy to carry out, product characteristics homogeneousAnd stable;
(3) preparation method of the present invention is without adding any catalyst in course of reaction, and reaction condition is simpleAnd economical;
(4) preparation method's reaction efficiency of the present invention is high, just can obtain complete half fiber replacing under temperate conditionElement derivative, for the exploitation of hemicellulose provide technical support.
Brief description of the drawings
Fig. 1 is the two-dimentional nuclear-magnetism HSQC figure of the full Butyrylation hemicellulose of the embodiment of the present invention 1.
Detailed description of the invention
Below in conjunction with embodiment and accompanying drawing, the present invention is described in further detail, but enforcement side of the present inventionFormula is not limited to this.
Embodiment 1
A kind of room temperature homogeneous phase of the present embodiment is prepared the method for full acidylate hemicellulose, and concrete preparation process is as follows:
(1) under nitrogen protection, according to hemicellulose (xylan quality percentage composition >=55%) and solventMass volume ratio is that the ratio of 1:10 (g/mL) is dissolved in dimethyl sulfoxide (DMSO)/N-first that 15mL volume ratio is 2:1In base imidazoles mixed solvent, 80 DEG C of solution temperatures, dissolution time 4h, obtains hemicellulose solution;
(2), under nitrogen protection, be 4:1 according to anhydrous wood sugar unit mol ratio in acylating reagent and hemicelluloseRatio, acylating reagent butyric anhydride is joined in the hemicellulose solution preparing in step (1) to chamberThe lower stirring reaction 12h of temperature;
(3) after esterification finishes, the solution obtaining is poured in the ultra-pure water of 150mL and precipitated, filter;Again the precipitation obtaining is dispersed in the ultra-pure water of 10mL and dialyses 7 days, after freeze drying, obtain full acidylate half fiberElement.
Calculate through hydrogen spectrum, the substitution value of the full acidylate hemicellulose that the present embodiment obtains is 1.98; Its two dimensionNuclear-magnetism HSQC collection of illustrative plates as shown in Figure 1. Fig. 1 is at 13.7/0.87ppm (Ca-Ha),18.1/1.50ppm(Cb-Hb)And 35.9/2.18ppm (Cc-Hc) signal located proved that the success of hemicellulose esterification modification carries out. SeparatelyIn HSQC collection of illustrative plates, there is not the anhydrous wood sugar of hemicellulose unit C-2 and C-3 position hydroxyl reaction outward,After signal, the full Butyrylation of hemicellulose has been described.
Embodiment 2
A kind of room temperature homogeneous phase of the present embodiment is prepared the method for full acidylate hemicellulose, and concrete preparation process is as follows:
(1) under nitrogen protection, according to hemicellulose (xylan quality percentage composition >=55%) and solventMass volume ratio is that the ratio of 1:20 (g/mL) is dissolved in dimethyl sulfoxide (DMSO)/N-first that 15mL volume ratio is 5:1In base imidazoles mixed solvent, 60 DEG C of solution temperatures, dissolution time 6h, obtains hemicellulose solution;
(2), under nitrogen protection, be 8:1 according to anhydrous wood sugar unit mol ratio in acylating reagent and hemicelluloseRatio, acylating reagent acetic anhydride is joined in the hemicellulose solution preparing in step (1) to chamberThe lower stirring reaction 6h of temperature;
(3) after esterification finishes, the solution obtaining is poured in the ultra-pure water of 150mL and precipitated, filter;Again the precipitation obtaining is dispersed in the ultra-pure water of 10mL and dialyses 7 days, after freeze drying, obtain full acidylate half fiberElement.
Calculate through hydrogen spectrum, the substitution value of the full acidylate hemicellulose that the present embodiment obtains is 1.95.
Embodiment 3
A kind of room temperature homogeneous phase of the present embodiment is prepared the method for full acidylate hemicellulose, and concrete preparation process is as follows:
(1) under nitrogen protection, according to hemicellulose (xylan quality percentage composition >=55%) and solventMass volume ratio is that the ratio of 1:8 (g/mL) is dissolved in dimethyl sulfoxide (DMSO)/N-first that 15mL volume ratio is 0.5:1In base imidazoles mixed solvent, 60 DEG C of solution temperatures, dissolution time 6h, obtains hemicellulose solution;
(2), under nitrogen protection, be 1:1 according to anhydrous wood sugar unit mol ratio in acylating reagent and hemicelluloseRatio, acylating reagent propionyl chloride is joined in the hemicellulose solution preparing in step (1) to chamberThe lower stirring reaction 48h of temperature;
(3) after esterification finishes, the solution obtaining is poured in the ultra-pure water of 150mL and precipitated, filter;Again the precipitation obtaining is dispersed in the ultra-pure water of 10mL and dialyses 7 days, after freeze drying, obtain full acidylate half fiberElement.
Calculate through hydrogen spectrum, the substitution value of the full acidylate hemicellulose that the present embodiment obtains is 0.43.
Above-described embodiment is preferably embodiment of the present invention, but embodiments of the present invention are not subject to above-mentioned realityExecute routine restriction, other any do not deviate from the change done under Spirit Essence of the present invention and principle, modification,Substitute, combine, simplify, all should be equivalent substitute mode, within being included in protection scope of the present invention.
Claims (10)
1. room temperature homogeneous phase is prepared a method for full acidylate hemicellulose, it is characterized in that comprising following preparation stepRapid:
Hemicellulose is dissolved in the mixed solvent of dimethyl sulfoxide (DMSO) and N-methylimidazole, obtains hemicelluloseSolution, then adds acylating reagent, carries out esterification under room temperature; After esterification finishes, by what obtainSolution is poured in precipitating reagent and is precipitated, and filters, and washing, obtains full acidylate hemicellulose after freeze drying.
2. a kind of room temperature homogeneous phase according to claim 1 is prepared the method for full acidylate hemicellulose, its spyLevy and be: xylan quality percentage composition >=55% in described hemicellulose.
3. a kind of room temperature homogeneous phase according to claim 1 is prepared the method for full acidylate hemicellulose, its spyLevy and be: the solution temperature that described hemicellulose is dissolved in mixed solvent is 60～120 DEG C, and dissolution time is0.5～6h。
4. a kind of room temperature homogeneous phase according to claim 1 is prepared the method for full acidylate hemicellulose, its spyLevy and be: the mass volume ratio of described hemicellulose and mixed solvent is 1:(5～30) g/mL.
5. a kind of room temperature homogeneous phase according to claim 1 is prepared the method for full acidylate hemicellulose, its spyLevy and be: dimethyl sulfoxide (DMSO) in the mixed solvent of described dimethyl sulfoxide (DMSO) and N-methylimidazole: N-methylimidazoleVolume ratio is (0.5～10): 1.
6. a kind of room temperature homogeneous phase according to claim 1 is prepared the method for full acidylate hemicellulose, its spyLevy and be: described acylating reagent is acetic anhydride, propionic andydride, butyric anhydride, chloroacetic chloride, propionyl chloride and butyrylAny one in chlorine.
7. a kind of room temperature homogeneous phase according to claim 1 is prepared the method for full acidylate hemicellulose, its spyLevy and be: in described acylating reagent and hemicellulose, the mol ratio of contained wood sugar unit is (0.5～20): 1.
8. a kind of room temperature homogeneous phase according to claim 1 is prepared the method for full acidylate hemicellulose, its spyLevy and be: the time of described esterification is 0.5～48h, course of reaction keeps uniform stirring.
9. a kind of room temperature homogeneous phase according to claim 1 is prepared the method for full acidylate hemicellulose, its spyLevy and be: described precipitating reagent refers to water; The addition of described precipitating reagent is 5～10 of reaction gained liquor capacityDoubly.
10. a kind of room temperature homogeneous phase according to claim 1 is prepared the method for full acidylate hemicellulose, itsBe characterised in that: described washing refers to the washing of dialysing in water.
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| CN201610010297.9A CN105601766A (en) | 2016-01-05 | 2016-01-05 | Method for preparing full-acylation hemicellulose at room temperature and homogeneous phase |
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| CN201610010297.9A CN105601766A (en) | 2016-01-05 | 2016-01-05 | Method for preparing full-acylation hemicellulose at room temperature and homogeneous phase |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115215943A (en) * | 2021-04-16 | 2022-10-21 | 中国科学院化学研究所 | Organic room temperature phosphorescent polymer material and preparation method and application thereof |
Citations (2)
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| CN103554522A (en) * | 2013-11-08 | 2014-02-05 | 南开大学 | Method for preparing solvent system capable of dissolving cellulose under room temperature condition |
| CN105001429A (en) * | 2015-07-08 | 2015-10-28 | 中国科学院广州能源研究所 | Mixed solvent for dissolving full components of lignocellulose and dissolving method |
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- 2016-01-05 CN CN201610010297.9A patent/CN105601766A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103554522A (en) * | 2013-11-08 | 2014-02-05 | 南开大学 | Method for preparing solvent system capable of dissolving cellulose under room temperature condition |
| CN105001429A (en) * | 2015-07-08 | 2015-10-28 | 中国科学院广州能源研究所 | Mixed solvent for dissolving full components of lignocellulose and dissolving method |
Non-Patent Citations (2)
| Title |
|---|
| FACHUANG LU等: ""Non-degradative dissolution and acetylation of ball-milled plant cell walls:high-resolution solution-state NMR"", 《THE PLANT JOURNAL》 * |
| 潘卫三等: "《工业药剂学》", 31 August 2015, 中国医药科技出版社 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115215943A (en) * | 2021-04-16 | 2022-10-21 | 中国科学院化学研究所 | Organic room temperature phosphorescent polymer material and preparation method and application thereof |
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Application publication date: 20160525 |